Ketonic acid-amine resins and process of making same



Patented Apr. 2, 1940 KETONIC ACID-AMINE RESINS AND PROCESS OF MAKINGSAME Almon G. Hovcy,

S. Hodgins, Royal Pleasant Ridge, and Theodore Oak, Mich., assignors toReichhold Chemicals,

Inc., formerly Beck,

Koller & Company, Inc., Detroit, Mich.

No Drawing. Application November 10, 1938, Serial No. 239,879

' 4 Claims.

The invention relates to ketonic acid-amine resinous condensationproducts and the process of making the same. The present application isa continuation-in-part of our prior application Serial No. 188,392 filedFebruary 2, 1938 (now Patent No. 2,149,678 dated March 7, 1939) which inturn is a continuation-in-part of an earlier application Serial No.147,569 filed June 10, '1937 (now Patent No. 2,153,801 dated April 11,1939).

The claims of the present application are directed specifically to theuse of laevulinic acid. and an organic amine and the fusing together ofthese components has been found to result in a particularly usefulresinous product.

There are a large number of patents on urea condensation products butpractically all of them cover tedious delicate processes requiring verycareful control of such conditions as pH and-temperature. Theingredients must be carefully reacted in a certain prescribed order andvery specific directions followed or else the product is likely to goover to a useless white insoluble precipitate, or else to a gel. Most ofthese patents covering urea resins are intended or mouldin purposes. Thepreparation of surface coating resins from urea is much more difficultthan the preparation of moulding compositions. Surface coating resinsmust be miscible with the commonly used paint, varnish and lacqueringredients. and requireskill not given in any publication heretofore.Furthermore, in the manufacture of urea resins it has not been possibleto make products which are as easy to cook or as foolproof inmanufacturing as the alkyd resins. It has. not been possible to makeresins by fusing urea or other amines with other reactive ingredients atrelatively high temperatures because gelation inevitably takes place attoo rapid a rate even for a rough control.

A fusion method would be highly desirable because it would avoidthetendency towards precipitation when an aqueous formaldehyde solutionis used and it would avoid dangerous formation of steam should thereaction run away." Furthermore,. the ,fusion method would allow the useof higher temperatures similar to those used in alkyd resin formationand with a much better chance. of obtaining resiniflcation than if thereaction were carried on in an aqueous solution.

We have found how to make resins-by such a fusion process, and we havefound that not only urea may be used, but a large variety of amines,

' including mono-amines, which hithertofore have been regarded asinoperative or unsuitable for .'any type of resin formation. Mono-aminesand other amines may have been suggested as modifying agents for resins,but havenever been considered as the basic resin-forming ingredients. Inour process, no control of pH is necessary, the 5 resinification takingplace under as orderly conditions as in the case of the alkyd resins,instead of requiring the meticulous control of artificial conditionswhich is necessary in the case of the urea-formaldehyde processes whichhave been l0 hithertofore described. It is not necessary that a solventor dispersing medium be present; our operations consist only of fusingthe ingredients, i. e., the acid and amine, Thus, the apparatus requiredfor carrying out our process is less complicated and less expensive. Theobvious simplicity of our process makes it especially desirable. Theincreasing availability and potential low cost of producing many aminesmakes our process even more desirable. 20

These resins are formed when various organic acids are reacted withurea, isobutyl amine or with several other amines, as shown by thegeneral reaction:

Amines Acid-#Resim Primary amines (R-NH:), +R'-l RgC-OH Resins Am'no comunds havin the eneral formula:

p0 HINY" NHJ-R+Rr-COH Resins where i v 1 groups. Y=a group snchas g -c-,0.11.- etc.

R =segment of hydrocarbon structure (alkylene or arylcne), e. g., 45

an alkyd-resin is disclosed which is obtained by and Engineeringequivalents, 1. e., thatthe trivalent nitrogen becomes pentavalent.

1. Ketonic acid+amine- "Ketacine resins 2. Unsaturate acid-l-amine-Unacine' resins 3. Dibasic' acid+amine Dib acine" resins 4. Hydroxyacid+amine- Hydrac ine resins- "These resins which weare describing arenot to be confused with the resins such as are de-' scribed in Weisbergand Greenwald U. 8. Patent No. 1,918,222, in which a resin which isessentially fusing phthalic anhydride'with triethanolamine. In case the.triethanolarnine is simply described as'another polyhydric body whichmight be used-as a substitute for glycerol, a trlhydric alcohol.Triethanolamine and phthalic anhydride should form a resin in exactlythe same way 'and according to the same principle as does glycerol andphthalic anhydride as described by Kienle' and Hovey (Journal of .TheAmerican Chemical Society, volume501, page 512,- (1929)).

We have found that amines without any hydroxyl groups form resins withthe organic acids of the generic formula R- I R2 COOH (as mentionedpreviously), this being an entirely unexpected result which is entirelyoutside the classification of alkyd resins, the definition of an alkydresin by Kienle and Ferguson being a fproduct of polybasic acids andp'olyhydric alc Chemistry, volume 21, pages 349-52, (1929)).

This application is one of a series iriwhichresins made from amine andvarious types of organic acids are-described. The present'applicationconcerns itself with .the resins formed hereafter in this applicationshall be termed' from amine and ketonic acid. These new and usefulresins are formed by simple fusion withj of using catalysts and. without4 the, necessity of carrying out the reactions in out the necessitysolvent or in the presence of a fluxing medium of any sort, and withoutthe necessity of controlling pH. For the sake of simplicity, theseresins formedfrom keto'nic acid and amine have been contracted to theterm Ketacln'e" resins, and

. Ketacine resins.

' where R=an alkyl or aryl group and R'=an alkylene oriarylene group Theketonic acids which form "Ketacine" resins with amines according to'our' invention come under the classification of the following generalformula:

nconfcoon carbon "atom length may bet to m Specific examples of thisgeneralformula are: I

Pyruvic acid, CH3.CO.COO H Aceto-acetic acid, CH3.CO.CH2.COOH

Benzoylbenzoic acid, CcHs.CO.CsH4.COOH l Benzophenone-dicarboxylic acid,

- CsH5.CO.CcH 3.(COOH)2 Benzoyl acrylic acid, mmcocmcrrcoon lParamethylisopropylorthobenzoylbenzoic acid,

= amen (can-1) .CO.CH4.COOH.

The following table giving many general exmples of how' various types ofresins may be] Prepared according to our. invention by fusing ketonicacids with a'mi-n'es, permits one to gain some idea of the breadth ofthe Ketacine of resins together with some idea of their 1m portancez'hols (Industrial ization. This is shown by the following ,tablez GENERALEXAMPLES.

Table I acid-l-urecoRed-orange resin acid-lrisobutylamine-oYellow-orange resin acid-aniline- Yellow-orange resinacld-heramethylcne tet'rsmine-Red-orange resin acid--formamide-Red#orange resin Pyruvic acid--succinimide+Yliow-orange resinPyruvlc acid-*thiourea-Black resin II Agata-acetic #23 8235!+lsobutylaminevLight straw colored resin I Benzoylbonmic acid+acetamido"Grcen resin gg 'gzi g +anllinevYellow-orange resin I fifgz g'}+hexamethylene tctramine' Dai-k' brown resin Bcnzoylben- .zoic acidBensoylbenzolc acid Benzoylbenzolc acid 31? 1'Z myummc wam-wmc resin zii}+diamylamine -*Browu resin 31 3531 +triamylamineoYellow resin I 221?iii? hyl omlne water-white resin g gg g i}+dimethylamine vWater-whiteresin 231 Q; +trimethylaniine oWatcr-white resin a i: 321 :1 +Dy lno-Water-white resin The following are specific ei ramples of' howKetacine" resins may befprepared according to our invention:

, Exmns .I

one 'mol'ot .urea is reacted with onemol of benzoylbenzoic acid at 150C. The ingredients were heated'to 150 C., in 10 minutes and then I heldat 150 C. for 30 minutes or longer. As the reaction proceeded the acidnumber decreased and-the color of the resinous products changed fromwater-white toy'ello'w'. The maturing of the resinis shown by the factthat the curing I time on a hot plate at 200 0. decreased from 25seconds to 2 seconds necessary to obtain gelatin- I Table 1r I CHANGE INACID NUMBERAND CURE 0F AI'RE'SIN roman) raou ONE MOL BENZOYL nnnzorcACID AND own nor. cam

Add Ooiorof' number 7 product 164 25- Water-whlte.

12 Do- 132 9 Pale yellow. 115 8 Yellow.

98 6 Do. 88 2 Do.

no minutes were required touse tbs materials and obtain 0. Y

' trio: plate temperature 200 When to the colors modifications of thisfamily of resins maybemade to form new products with new and-still 4 Itisto be understood parts of urea are in combination with which unknownto the art, a colored product is obtained.

Exmtr: II

much lighter To one mol of benzoyl'benzoic acid, two mols.

of isobutylamine' are added. An exothermic reaction takes placewhich-warms the mixture of ingredients to approximately 70C. Theseingredients are-= allowed to'react from their own,

heat for a period of -30 minutes and then when the reaction has run itscourse, the reaction may be carried further by supplying heat to thereaction mixture. The heating is best done at about 150 C. using areflux condenser to prevent the escape of isobutylamine. When therefluxinghas proceeded far enough so that'there is no odor'ofisobutylamine the condenser may be removed and heating discontinued.This process forms a pale straw colored resin'. This material wassoluble, while hot, in mineral spirits about one volume to onevolume,'but when it cooled the resin precipitated from solution. -Whenthis material was thinned with butanol, it formed a very stable solutionwhich blended with practically all of the commercial types of alkydresins even i if they were already cut 50% in mineral spirits.

This family of'resins made from ketonic acids and amines may be modifiedby other ingredients to vary the properties in much the same way thatallwd resins made from'polybasic acids and polyhydric alcohols havebeen-modified withthe fatty acids, resinous acids and phenoliccondensation products. It will be understood that many such furtheruseful properties. that such modifications also 'comeunder the scope ofthis invention.

On the other hand,if one should usef Ketacine" resins to modify otherresinous products, these uses of the Ketacine resins are to beconsidered as applications of this invention and also includedby it. 'Asan example for a use of our invention to modify other resinous productsthe following is cited as illustrative:

The resin made from benzoyl benzoic acid and I isobutylamine as shown inExample II is used densation process. 200 parts of the resin prepared asin Example II. and 62 parts of formaldehyde (commercial solution37-40%). and 30. reacted together. First the formaldehyde is added tothe resin made from benzoyl benzoic acid and isobutylamine" and a cloudywhite precipitation occurs during the initial stages of reaction. butthis soon clears up between 50-60- C. When the formaldehyde is added thetemperature rises from room temperature to 50-10 C. Upon adding 30 partsof urea the. solution became somewhat cloudy and clear ,unon graduallyinviscous, but it becomes v creasing the temperature to 95 C. andholding at this temperature.

clear. when. the desired viscosity is obtained the material may bethinnedwith butanol to a- 60% solution.v clear straw colored. viscoussolution in butanol is miscible with all types of commercial alkyd resinsolutions such as the oil or oil acid-modified types of polybasicacid-poly, hydric resins in solution form, using hydrocarbon.

solvents either of the aromatic or aliphatic types.

The product is soluble in butanol, xylol or toiuol proportion andsoluble to apto practically any parts by proximately equal theurea-formaldehyde con- The material becomes more and more viscousand-continues to remain during the reaction.

volume in mineral were fused with 1 mol of urea' (60 parts byweight) for3 minutesat 100 C'; The reaction was fast and the product had tobechilled to prevent gelation occurring, but no. foaming tool: place. Thelight yellow-orange-resin resulting had a softening point of "-35 C. andconverted to the infusible state very rapidlywhen heated 8 C. It wascom:-

seconds on a hot plate at 200 pletely soluble in water without heating,slightly soluble in alcohol, and insoluble in ,-acetone, toluol, and inmineral spirits, and was soluble in alcohol upon heating. ness andadhesion to glass and very fast curing properties together, withsolubility in water, it is apparent that this resin has special value inwater soluble adhesives or in combination with various glue solutionsfor use in furniture glues,

plywood glues, laminated material and the like.

EXAMPLEIV Y were allowed "to react with 1 mol- ('73 parts by weight) of-is obutylamine. The reaction was very noticeably exothermic. It was notnecessary to suply heat during the early stagesof the reaction. Thetemperature rose to approximateminutes, a very dark red, sticky balsamresulting, which converted ,to .the infusible state on the hot plate in9-10 seconds at 200C. It was only slightly soluble in water, soluble inalcohol, slight- -ly soluble in acetone and in toluol, but'insoluble inmineral spirits. This product is particularly On account of itstoughhave had a chance to One mol of pyruvic acid (88 parts by weight)ly 90C. and was held at that temperature for. 13

useful as a resin plasticizer-for spirit varnishes,

shellac, and other natural-alcohol-soluble resins which in themselvesare too brittle.

r ExAmPL nVI 0ne mol of pyruvic. acid was heated. with 1 mol ofdiethylene triamine (120 parts by weight).' Reaction took place with-(88 parts by weight).

out. foaming as the temperature was gradually advanced up to 210? C.within 40 minutes.- The color'developed from yellow; at 180 C.-to darkbrown when held 40 minutes at 260 C. The final product had a hot platecure of 12 seconds at 200 C., and was soluble in water, denaturedalcohol, acetone and, toluene,- but was insoluble in mineral spirits.The-resulting balsam is of value as a resin plasticizer for manycoatings.

types: of surface ExAmrL'r: yr

One mol' of la evulinic acid (116 Pparts by weight) were; fused with onemol of urea (60 parts by 'weight) for 30 minutes at -155PC. No foam tookplace to anydangerous, extent transparent orange colored resin had asoftening range of 35-40" C., and was a hard, tough resin, having goodadhesion to glass and converted to the infusible. statelby heating for18 seconds at 200" C. in thin films. It :waslsolublein water, denaturedalcohol, and insoluble inacetone, mineral spirits, and in toluol.

This resin is useful The resulting clear, bright, I

Y One mol of laevulinic acid (116 parts by isapparentthattiiisr ihusiriadeinthisexin spirit varnishes, and for toughening shellac clearlydifferent from that which is described by and other alcohol solublenatural resins. Grimaux, Annales de Chemie et de Physique. 5th W Series,vol. 11, pages 373-389 (1877), who merely mentions an amorphous whitepowder which is On 1 1 O lae llni i 16 Pa bywelght) insoluble inalkalis. Our product of reaction of were fused for 25 minutes at 155-200C. with 1 pyruvic acid and urea obtained by fusion remol ('73 parts byweight) of isobutyl amine, a suits in a very fast curing, water-solubleresin. red, viscous balsam resulting, which had a 55 Grimaux does noteven describe his product as a second cure on a 200 C. hot plate andpossessed resin, He did not recognize it as a resin and insolubility inwater and in mineral spirit, but knew nothing of the value oftheproduct. Our complete solubility in alcohol, acetone, and in product isclearly differentiated from Grimauxs toluol. This resin is of value as aresin plasin thatdt is a resin which may be easily recogticizer for agood many of the commonly used nized assuch, and in addition it is heatconvertimaterials inthe coating and the plastic indusble. All omtheother examples, of course, are tries on account of its solubility in thecommonly clearly not .to be confused with Grimauxs or used solvents, itsstickiness, its high viscosity any of the other disclosures in theliterature, which works against loss of plasticizer bymigraparticularly, the examples which contain isobut'yl tion, and onaccount of its freedom from evap- 111111116, it never before v n e ho htD oration, as most chemical plasticizers are much sible to form resinsfrom a mono-amine as a more volatile than desired. principal reactingingredient. The following tabulation based on Examples vm III to VIIIwillv give further information regarding the process and the resultingproducts:

H t s01 bllit i i t'eo y i 0 u y o nsouti mm Grams Amine Grams FoamingColor wing 2 01?) No.. add 0., e pgicnt. (m) I I 200C. Wa- Ace- M. Tol-Color tar tone 8. uol HK T-7 6l-A Pyruvie Urea 100510. No Orange -30 8"8 S18 -1 I I I 130 Cloudy B Pymvic IDA I8 90C. Very Dark 9%" 81B S 815 I513 A, 9

13' reactive red C without heat C Pyruvic 22 Die I- an 111F195 N0 Black12 S S 8 I S '(A 9 en 7 yellow D Lacvulinie Urea l5 llgaltli No Orangel8" s 8 I I I A, 6-7

E mvlflinlc IBA' 18 151-200 N0 Rad I S S I S (A 7-8 25/ -F Laevulinie 29Dieth 1- so B011! N0 Red 8" B S B 818 Sis AB 9' ano- 154 (dark) i l l l81S tl l bl Linaol bl to 1 th o Jon 0; ysou e' u e grea rthm: ess an.

M..s. designates mmsgg mu mvu'l a boiling iani e oi aw -400' a a Kauributanol value 0136.

weight) were fused for 30 minutes at 154-161 C. Products made alongorthodox varnish and with 1 mol of diethyle'ne trial nine parts byweight). The reaction was not violent, showing no uncontrollablefoaming, and it was-necessary to supply heat to keep the resin-formingreaction soing. At the end of 30 minutes of heating the color of theresinous balsam had changed from red to a very dark red so that, uponlooking through about one-half inch of this material, it appearedbeautifully transparent and blood colored. The resinous balsam was avery-viscous liquid resin at room temperatureof about the consistency ofa. very slow flowing tar, but converted to the infusible state on a 2000. hot plate in 8 seconds, and was soluble in water, alcohol, andacetone and slightly soluble in toluol and mineral spirits. On accountof its high viscosity, quick thermo-setting properties, and'lowpenetration in the paper, and other properties whichwillberecognizedbythoseskilledintheart,it

family are to be considered as applications of this resin family and tobe coveredby the scope of this invention. It is to be further understoodthat certain catalysts-may be used to promote further resiniflcation ofthese ingredients or to accomplish this purpose in a shorter'time, Insome caseswhere resins .form with difilculty we have foundit especiallyhelpful to introduce such isobutylamine and pyruvic acid, in which theresinification may be speeded up materially by the use of a catalystalthough such catalyst is not essential. We anticipate that any processwhich undertakes the simultaneous reduction of a nitro resinifying theresulting amine with a ketonic For-example, we have shown that aniline,the

resin with ketonic acid.

ample, has value in the printing ink industry as v In surface coatingssuch as lacquers and varaveryfastdryinginkingredient.

Notes-The product in Example III ls'very a catalyst. An instance of thisis in the case of acid to be within the scope of our invention.

reducticnproduct of nitrobenzene can form "a nishes these resins; onaccount of their adhesive lacquer technology with resins of theKetacinefl compound to an amine and at the same time i properties,increase the value of surface coatings, being aliphatic, aromatic orhaving mixed aliespecially lacquers, where they increase adhesion,toughness and hardness of the resulting product. The usefulness of theseproducts is not limited to surface coating materials as it extends intoplastic moulding compounds aswell and particularly into rubber sincethey reduce the porosity of rubber and increase the adhesion and tend toact as antioxidants and, in the case of the thiourea Ketacine" resins,they tend to act as vulcanization accelerators as well. Many of theseresinous products are characterized by extremely light color and colorretention.

The Ketacine resins are thermo-setting and 'heat convertible, and,particularly in the case of those manufactured from aliphatic ketonicacids such as pyruvic and laevulinic acids, are useful as components ofadhesives, cementing compositions and surface coatings generally.

By the term ketonic acid as used in the present specification and claimswe have reference to organic acids derived from ketones, such acidsphatic and aromatic radicals.

By the' term amine as used in the present specification and claims wehave reference to that class of strongly organic amine and laevuiinicacid, said acid and said amine constituting the principal reactingingredients.

3. An' artificial heat-setting resin formed by fusing together anorganic mono-amine and laevuiinic acid. I

4. An artificial heat-setting resin formed by fusing together an organicpolyamine and go laevulinic acid.

ALMON G. HOVEY. THEODORE S. HODGINS.

basic substances derived from 5 ammonia by replacement of hydrogen byone or

